Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates.

The very limited number of structurally known thionitrosyl complexes of technetium was increased by the synthesis of [Tc(NS)Cl(PPh)] () and [Tc(NS)Cl(PPh)(OPPh)] () and their reaction products with hydrotris(pyrazolyl)borates, {HB(pz)}. Similar reactions were conducted with [Tc(NO)Cl(PPh)(CHCN)] and related rhenium thionitrosyls. Remarkably, most such reactions result in a rapid cleavage of the boron-nitrogen bonds of the ligands and the formation of pyrazole complexes of the two group 7 metals.

[Tc(NO)(Cp)(PPh)Cl] and [Tc(NO)(Cp)(PPh)(NCCH)](PF), and Their Reactions with Pyridine and Chalcogen Donors.

Reactions of the technetium(I) nitrosyl complex [Tc(NO)(Cp)(PPh)Cl] with triphenylphosphine chalcogenides EPPh (E = O, S, Se), and Ag(PF) in a CHCl/MeOH mixture (/, 2/1) result in an exchange of the chlorido ligand and the formation of [Tc(NO)(Cp)(PPh)(EPPh)](PF) compounds. The cationic acetonitrile complex [Tc(NO)(Cp)(PPh)(NCCH)] is formed when the reaction is conducted in NCCH without additional ligands. During the isolation of the corresponding PF salt a gradual decomposition of the anion was detected in the solvent mixture applied.